Process for treating carbonaceous materials



Patented Nov. 10, 1931 T.

' UNITED STATES rnoonss ron TREATING cAn oNAcEoUsnArnRrALs narmsenn PETROLEUM mAArscHArrIJ, on THE HAGUE, NETHERLANDS PATIENT or-Pica HEIN ISRAEL WATERMAN, F DELFT, NETHERLANDS, .ASSIGNOR TO DE No Drawing. Application filed June e, 1929, Serial No. 369,004, and ili the Netherlands m a, 1928. f

The present invention involves a process for the manufacture of liquid products from coal or other carbonaceous materials and for the liquefaction of these raw materials.

The object of the invention is to obtain or render possible a maximum conversion of the said materials into liquid products by the known method according to which the primary substances are exposed to the action of hydrogen or gasesor vapours containing hydrogen under a high temperature and pressure and in the presence of a contact mass or catalyst. I

In particular the invention concerns a catalyst eminently suitable for the above-mentioned process.

In the French Patent No. 618,490, attention is drawn to the favourable catalytic effect exercised upon the hydrogenation process by an alkaline, iron oxide-containingmass known commercially under name of Luxmass,

which is obtained as a by-product from the wet-treatment of bauxite to aluminium-oxide, This mass is an alkaline iron oxide-containing mass which is obtained as a by-product from the conversion of bauxite to aluminum oxide by the wet treatment and is employed for purifying illuminating gas. stance, Ullmann Enzyklopadie der technischen Chemie, 1st edition, vol. 1, p. 314.)

It has now been discovered that this Luxmass can be brought into a state in which, in comparison with the original mass, it has a more favourable effect upon the process of hydrogenation, that is to say the percentage of coal remaining after hydrogenation is considerably smaller than in the case with the original Luxmass.

I have found that when commercial Luxmass is treated as will be described more fully hereinafter, its catalytic effect on the process mentioned above is considerably increased.

The treatment according to my invention consists in washing Luxmass either once or several times with water either at ordinary or at higher temperature, whereby certain substances are removed and a mass is obtained which acts better catalytica-lly than the original mass. a

(See, for in- I As examples of thetreatment of the Luximass the followingmay serve:

I. 40 grammes of the mass containing 36.6 grammes dry substance, was treatedand retreated von the steam bath with about i 0.5 litre water at a time,after'settling the liquid was-pouredof'f. 7 l

The mass was then filtered and dried at about 120 C. It was found thatin this manner 13.4% of the original dry substance treated had been removed. a

205 grammes Garisborg brown coal,.with a content of 181.5 grammes dry and ashfree coal, were brought into an autoclave together with 15.4 grammes of the mass prepared as describedabove containing 1.5 grammes of waterand 13.9 grammes dry substance. The mass was heated in the presence of hydrogen under an initial pressure of 100 kg./cm. to p a temperature of about 450460 C.

Calculated on dry and ashfree brown coal, the reaction products comprised 6.7% hydrocarbons boiling up to 220 (1., 8.6% hydrocarbons boiling between 220300 C., 4.9%

phenolic substances boiling up to 300 0.,

39.3% of a heavy asphaltic residue and 3.4% of coke.

An analogous experiment was carried out with an equivalent quantity of the original Luxmass, whereby the following yields were obtained: 4.9% hydrocarbons boiling up to 220 (3., 5.5% hydrocarbons boiling between 220300 (1., 3.8% phenolic substances boiling up to 300 0., 39.6% of a heavy asphaltic residue and 13.0% of coke.

ple I, but in the presence ofthe same amount From a comparlson of the two experiments of the finer-grained particles obtained as described above. The yields calculated on ashand moisture-free brown coal were as follows: 6.4% hydrocarbons boilin up to 220 (3., 6.1% hydrocarbons boiling between 220 and 300 0., 4.1% phenolic substances boiling up to 300 0., 45.2% heavy asphaltic residue, 3.6% of coke.

The use of the catalyst according to this invention is in no way restricted to any special manner of carrying out destructive hydrogenation but can, be applied advanta geously in all processes whereby carbonaceous 7 materials are exposed to heat and pressure in the presence ofhydrogen or hydrogencontaining gases for the purpose of obtaining valuable products therefroin' What I claim is:

A process for treating carbonaceous materials in the presence of hydrogen under elevated temperature and pressure for ob-' taining valuable products therefrom, comprising the step of subjecting the initial materials to destructive hydrogenation in the presence of a. mass derived from an alkaline iron oxide-containing mass obtained from the conversion of bauxite to aluminum oxide by the Wet-treatment by removing water-soluble substances therefrom.

. In testimony whereof I have afiixed my signature. HEIN ISRAEL WATERMAN. 

